The presented work is devoted to the study of the possibility of using planar materials consisting of ultramicroelectrode arrays for voltammetric analysis of compounds with close redox potential, but with different diffusion coefficients, which has great prospects in the analysis of various oligomers, including oligopeptides. A feature of the electrochemical behavior of materials containing arrays of ultramicroelectrodes is the realization of hemispherical diffusion, which can lead to the steady state or unsteady state regime of the electrode depending on the intersection or non-intersection of the hemispheres. There is also a
transient mode of operation of electrodes at partial intersection: voltammetry diagrams obtained in this mode may contain analytical information on the concentrations of substances with one redox potential, which favorably distinguishes the approach from the classical cyclic voltammetry using macroelectrodes. The prospects of the proposed approach are confirmed by the
example of analysis using ultramicroelectrode arrays of ferrocenemethanol and triglycene ferrocenemethanol ester. The results obtained prove the possibility of applying the approach to the analysis of electroactive oligopeptide derivatives.